WO2011110333A1

WO2011110333A1 - Building material with thermally insulating properties

Info

Publication number: WO2011110333A1
Application number: PCT/EP2011/001151
Authority: WO
Inventors: Handl Werner
Original assignee: H.C. Carbon Gmbh
Priority date: 2010-03-10
Filing date: 2011-03-09
Publication date: 2011-09-15
Also published as: WO2011110333A4; EP2545108A1; DE102010010957A1

Abstract

The invention relates to building material having thermally insulating properties, wherein the building material contains particles (1) of petroleum coke, in particular calcined petroleum coke, and the building material is a nonmetallic inorganic material and/or a natural material and/or a synthetic polymer apart from polystyrene.

Description

BE S C OPENING G BAUMATERIAL WITH HEAT-INSULATING PROPERTY

Technological background

There are many building materials with heat-insulating properties. In order to obtain sufficient thermal insulation properties in the construction sector, ever greater efforts are being made. Usually, conventional building materials additives are added, which reduce the thermal conductivity and thereby improve the thermal insulation of the building material. In addition, there are other requirements for building materials, such as increased reflection of infrared radiation (heat radiation and / or cold radiation) and protection against electrosmog.

State of the art

From WO 2008/089085 Al a building material in the form of a fiberglass material is known, in which the fibers are provided with a graphite coating in order to avoid electrostatic charging of the fibers. The coated fibers are used for insulation purposes in a wide variety of applications.

From EP 1 749 805 a gypsum building material with increased thermal conductivity as well as a shielding effect against electromagnetic radiation is known. The gypsum building material is added to a regrind of compacted graphite expandate.

CONFIRMATION COPY From WO 2005/120146 a brick with cavities is known, the cavities are coated with a reflective of an electrically conductive and / or infrared radiation material, wherein the material is graphite or mica.

From DE 20 2008 014 415 Ul as well as from EP 2 028 329 AI a heat-insulating brick with cavities is known in each case, the cavities are filled with a thermal insulation material. A polymer foam is known from DE 197 28 543 A1, to which graphite is added as an additive for reducing the thermal conductivity.

WO 97/45477 discloses expandable styrene polymers which, based on the weight of the polymers, contain 0.05 to 25% by weight of carbon black particles in homogeneous distribution and are processed to self-extinguishing foams having a density of <35 g / l can.

EP 0 372 343 A1 discloses a polystyrene foam which contains soot particles having a particle size of from 10 to 100 nm and a specific surface area of from 10 to 1500 g.

From WO 2008/141767 A2 it is known that a composite material based on vinylaromatic polymers to increase their thermal insulation properties particles of graphitic material, such as graphitized coke, with a degree of graphitization of at least 0.2, preferably a degree of graphitization of 0.3 to 0.95, add.

Synthetic graphite is produced by a thermal treatment at temperatures of about 2,800 ° C. The production of synthetic graphite is therefore especially energy intensive. In addition, there is also natural graphite, which mined and processed by mining. Both synthetic and natural graphite are suitable for reflecting IR radiation. However, graphite has a comparatively higher thermal conductivity, which adversely affects the insulating effect of the building material when touching the graphite particles within the matrix (percolation).

task

The object of the present invention is to provide a novel building material with improved properties.

The above object is achieved in that the building material contains particles of petroleum coke, in particular calcined petroleum coke, and it is the building material is a non-metallic-inorganic material and / or a natural material and / or a plastic other than polystyrene.

The use of petroleum coke, in particular calcined petroleum coke, has the following advantages:

(a) calcined petroleum coke has a much more favorable energy balance compared to synthetic graphite, as only a much lower temperature of about 1200 ° C is necessary for the calcination of petroleum coke;

(b) Calcined petroleum coke has a significantly lower thermal conductivity compared to synthetic or natural graphite, which means that when the percolation threshold is reached, a significantly lower increase in the CO 2 is achieved compared to synthetic or natural graphite Thermal conductivity sets, so that the thermal insulation of the component is only slightly influenced. In practice, unavoidable island-like particle accumulations within the component (so-called "percolation islands") often occur.For this frequently occurring case, the use of calcined petroleum coke compared to graphite is particularly advantageous since it is compared to calcined petroleum coke due to the poorer heat conductivity (c) calcined petroleum coke, in contrast to graphite, is brittle and, for this reason, easy to grind, ie to bring into the required particle shape;

(d) calcined petroleum coke can be converted to particles of platelet form by use of suitable milling techniques;

(e) in contrast to carbon black, which has a very high specific surface area, the use of calcined petroleum coke particles has the advantage that, for the required thermal insulation effect, particles with a much lower surface area compared to carbon black are available; this has the advantage that, unlike e.g. in soot, flame retardants, which are for certain

Building materials must be provided imperatively, can not be absorbed through the surface. For this reason, it is possible to use a comparatively small amount of flame retardant. Flame retardants are extremely expensive;

(f) Petroleum coke, especially calcined petroleum coke, also provides shielding against electromagnetic waves, electrosmog, and the like. The petroleum coke is expediently calcined petroleum coke, which is thermally treated at a temperature of about 1200 ° C. In this case, the volatiles present in the so-called green coke escape. For calcined petroleum coke there is no graphitization (0% degree of graphitization).

Particularly suitable are anisotropic petroleum coke particles.

Good efficiency is obtained when the petroleum coke in the form of needle coke, suitably anisotropic needle coke particles present.

A particularly good efficiency arises when the petroleum coke particles have a platelet-shaped grain shape. They then act in the matrix of the building material like a multitude of tiny, disorderly arranged mirrors, which bring about optimal reflection of infrared radiation (thermal radiation or even cold radiation).

The petroleum coke particles advantageously have a particularly high aspect ratio, which is in particular in the range from 1 to 500, preferably from 5 to 50, the aspect ratio representing the ratio of the average diameter to the average thickness of the particles.

Advantageously, the petroleum coke particles may have a mean particle size of 1 μπι to 50 μπι, preferably from 1 μηι to 10 μηι.

Conveniently, the petroleum coke is added in such an amount based on the total weight of the building material, that the thermal conductivity of the building material depending on the building material in question compared to a corresponding building material without petroleum coke is reduced by at least 2.5%, preferably by at least 10%, particularly preferably by at least 20%.

It is particularly advantageous if the petroleum coke is contained in an amount of 0.05% by weight to 10% by weight, based on the total weight of the building material.

If it is a building material with a binder such as e.g. Mineral fibers, e.g. are fixed by means of resin to a fiber composite, or insulating materials made of natural fibers, in which the natural fibers are bound with a suitable binder, the petroleum coke particles are added to the binder, so that they are uniformly distributed there.

Alternatively or additionally, the respective fibers or fiber mats may each be provided individually or in combination with a petroleum coke particle-containing coating. This can be done either by impregnation, dipping, spraying or similar technology. The petroleum coke particles are expediently dispersed in a binder or a binder solution. Particularly advantageous for this purpose is a thermally or hydraulically curing binder.

According to another embodiment of the present invention, a petroleum coke particle-containing coating is used in a building material in the form of a fired shaped body. Preferably, the coating is in the region of the walls of the mold cavities of the shaped body.

Conveniently, the mold cavities of the molding can be completely filled with petrolkoksbeschichteten fibers. Alternatively, the building material is a hydraulically bound shaped body, for example a concrete block or a molding containing gypsum. In both cases, the addition of petroleum coke particles causes a significant improvement in thermal insulation.

Alternatively, the building material is a pasty, viscous mass capable of being applied by the user by brushing or trowelling. Alternatively, the building material is foamed polymer material, which is preferably used as mounting foam and / or insulating foam. Again, the use of petroleum coke particles contributes to a significant improvement in the insulation effect. For example, in a two-component system, the petroleum coke particles may preferably be added to one of the starting components or, e. in the case of moisture-reactive polyurethanes, be added directly to the reaction component. When applied from the aerosol can, the petroleum coke particles are distributed in the membranes of polyurethane foam and thereby improve the thermal insulation significantly in window or door frame assembly or other Ausschäumvorgängen.

Embodiments of the invention

Advantageous embodiments of the invention will be explained in more detail with reference to drawing figures and examples.

Show it: a highly simplified, schematic representation of an arrangement of petroleum coke particles in a matrix;

2 shows a greatly simplified, schematic illustration of a fiber-containing Dämmmatte insulating mat (Fig. 2A), an enlarged partial section of

Insulating mat (FIG. 2B) and a detailed representation of the individual connection points of the fibers of the insulating mat (FIG. 2C);

3 shows a greatly simplified, schematic cross-sectional representation of a second embodiment of a fiber-containing insulating mat;

Fig. 4 is a highly simplified, schematic cross-sectional view of a first

Embodiment of a molded body; 5 shows a greatly simplified, schematic cross-sectional representation of a second embodiment of a shaped body;

6 shows a greatly simplified, schematic cross-sectional illustration of a third embodiment of a shaped body;

Fig. 7 is a highly simplified, schematic cross-sectional view of a first

Embodiment of a gypsum board;

8 shows a greatly simplified, schematic cross-sectional view of a second embodiment of a gypsum board;

9 is a highly simplified, schematic cross-sectional view of a with

Petroleum coke particles coated fiber (single fiber (Figure 9A)) as well as a petroleum coke particle coated packing (Figure 9B); such as 10 shows a greatly simplified schematic illustration of a spiral jet mill with high-performance air classifier (FIG. 10A) and a greatly simplified, schematic snapshot of the flow containing petroleum coke particles in the spiral jet mill (FIG. 10B).

According to the invention, petroleum coke particles, in particular particles of calcined petroleum coke, are used to increase the thermal insulation. Petroleum coke is a residue of petroleum distillation and is produced in so-called crackers. The calcination frees the petroleum coke from volatiles and gives it purity levels of 99% carbon. Petroleum coke can thus be regarded as carbon, but does not belong to the ätiotropic forms. Calcined petroleum coke is not graphite. Nor does it possess any degree of graphitization since it has no displaceable layers. Also, it can not be counted among amorphous carbons such as soot. For example, petroleum coke has no typical lubricating effect with respect to graphite and only poor electrical and thermal conductivity. Depending on the production method, anisotropic or isotropic cokes are produced. According to the present invention, isotropic petroleum cokes are preferred. These are usually freed of volatile constituents by heat treatment, in the range of 1,200 ° C., in rotary kilns. This process is also referred to as calcination. Depending on the application, the calcined coke pieces are broken into small pieces or ground to powder in hammer mills. The petroleum cokes are used almost exclusively for the production of electrodes or in the steel industry as a carburizing agent. According to the present invention, calcined petroleum cokes are ground into platy powders. These platelet-shaped powder particles improve the thermal insulation of the building material, since they act in the relevant matrix like small, irregular mirrors and therefore the infrared radiation, ie heat or cold radiation, effectively reflect.

For the use of petroleum cokes as infrared blocker particularly isotropic cokes are suitable. For use as an infrared blocker in addition to the grain size and the grain shape of importance. In particular, a platelet-shaped grain shape shows particularly good thermal insulation values. According to the invention, such preferred grain shapes are made with delaminating mills. Such mills are eg ball mills or air jet mills, such as spiral jet mills. Particularly suitable are spiral jet mills, since they allow a particularly high proportion of platelet-shaped particles. The petroleum cokes according to the invention have a particularly high aspect ratio. The petroleum coke particles expediently have a specific surface area in the range from 3 to 50 m ² / g, preferably from 3 to 35 m / g, particularly preferably from 3 to 20 mVg. In the present invention, aspect ratio means the ratio of the average diameters to the average thicknesses of the particles.

The petroleum coke can preferably be comminuted in a hot-gas jet mill with high-performance air classifier for producing the petroleum coke particles with a platelet-shaped particle shape and a low specific surface area. In this case, high-pressure steam or hot air, preferably from an oil-free screw compressor, can be used as the gas. The gas temperature is preferably in the range of 120 ° C to 250 ° C. By suitable adjustment and geometry of the air nozzles and the air classifier (classifying wheel) particles with suitable average particle size can be obtained. Figure 10A shows in a simplified representation of the principle of a spiral jet mill with attached air classifier.

10B shows the tangential inflow of gas 20 via correspondingly arranged nozzles 21 for generating a tangential flow 22 which spirally accelerates the particles 1 along the spiral jet mill 19, whereby the particles 1 are comminuted and slowly depending on their size to the center of the spiral jet mill 19th move and be discharged there via the air classifier 23 on reaching the appropriate grain size. By applying this particularly delaminating grinding technique, the platelet-shaped particle shape is achieved.

Conveniently, the average particle size is in the range of 1 μπι to 50 μηι, preferably 1 μπι to 25 μιιι, more preferably 1 μηι to 10 μηι. These are preferably used in the context of the present invention.

The petroleum cokes according to the invention have an aspect ratio between 1 and 500, preferably between 5 and 50.

Advantageously, the petroleum coke may be present in an amount of 0.05% by weight to 10% by weight, based on the finished body or shaped body, so that the correspondingly reduced thermal conductivity is established.

The thermal conductivity of the building material with petroleum coke compared to a corresponding building material without petroleum coke may be reduced by at least 2.5%, preferably by at least 10%, particularly preferably by at least 20%. Fig. 1 shows only in a highly simplified, schematic representation, the arrangement of two platelet-shaped petroleum coke particles 1 as an example of a plurality of corresponding particles in a suitable matrix 15. By matrix 15, for example, a binder, a mass offset or the like can be understood. The petroleum coke particles 1 are randomly oriented and therefore act as small reflection mirrors that reflect heat or cold jets 3 and thus improve the thermal insulation of the building material.

Figs. 2A to 2C show the use of petroleum coke particles 1 in a fiber insulating mat 4. Reference numeral 5 denotes the respective fibers, e.g. Glass fibers, stone fibers or natural fibers, e.g. Wood fibers. On one side of the fiber insulating mat 4 is a liner 16, e.g. in the form of an aluminum foil, provided. The fibers 5 are distributed randomly, the air between them serves as insulation.

The individual fibers 5 are connected according to FIG. 2B in the region of their contact points by means of a binder containing petroleum coke particles 1.

FIG. 2C shows, in a greatly simplified, exemplary representation, a linking point of two fibers 5 which is embedded in a binder 2 containing petroleum coke particles 1.

When using mineral fibers, especially glass and / or rock wool, resins such as e.g. Used phenolic resins.

Instead of adding the phenolic coke particles 1 in the binder 2, it is also possible to disperse the petroleum coke particles 1 in a binder 2 or in a binder solution and then to fibers 5 or fiber composites with the dispersion by impregnation, dipping, spraying or the like loading layers. A correspondingly coated fiber 5 is shown in the illustration of FIG. 9A.

A fibrous insulating mat 4 coated on both sides with a petroleum coke particle 1 coated layer 6, 7 is shown in FIG. The layer 6 or 7 can also be formed by impregnation, dipping, spraying or the like.

The binder 2 is preferably a thermosetting or hydraulically curing binder.

Alternatively, as the building material, an insulating mat, insulating board or insulating body based on binder-bonded wood fibers, natural fibers, e.g. be provided lignocellulosic fibers. The petroleum coke particles 1 are mixed into the binder and homogeneously distributed there. These are predominantly the following binders: urea-formaldehyde, melamine-urea-formaldehyde, melamine-urea-phenol-formaldehyde, phenol-urea-formaldehyde, phenol-formaldehyde and PMDI resins. Fig. 4 shows the building material according to the invention in the form of a shaped body, in which the petroleum coke particles 1 are embedded in the mass of the molded block 14. In particular, this type relates to so-called hydraulically bound stones, e.g. Concrete blocks in which the petroleum coke particles 1 are added directly to the concrete offset, so that the petroleum coke particles 1 are integrated into the mass of the molded block 14.

Alternatively, in the case of a shaped block, as shown in FIG. 5, the material containing the petroleum coke particles 1, in particular a heat-insulating mat or a multiplicity of coats coated with or coated with petroleum coke, may be present. Body or a petroleum coke particles containing foam may also be disposed within the mold cavity 8 of the molded block 14. In the embodiment shown in Fig. 5, the mold cavity 8 is completely filled. Alternatively, in the embodiment according to FIG. 6, only the inner wall of the mold cavity 8 is provided with a coating comprising petroleum coke particles 1.

The above embodiments according to FIGS. 5 and 6 are particularly suitable for fired bricks, such as e.g. Brick, but also for hydraulically bound bricks. To coat the walls of the cavities, a suspension of petroleum coke particles and binder is used.

Conveniently, the petroleum coke particles are metered within the suspension so that no percolation occurs.

In the same way, as shown in the embodiment of FIG. 7, petroleum coke particles may also be incorporated in a gypsum board 9. The gypsum board 9 comprises an outer layer 10 and inner layer 11, which surround a layer of gypsum 12. In the layer 12, the petroleum coke particles 1 are in an irregular arrangement.

Furthermore, as an alternative or in addition to the above embodiment, an additional layer 13 containing petroleum coke particles 1 can be applied to the outside of the gypsum board 9 (see FIG. 8).

Petroleum coke particles 1 can also be used in the context of the invention for coating packings 17, for example made of pearlite, expanded clay, vermiculite or mica, as shown schematically in FIG. 9B. Here are the petroleum coke particles are applied to the surface of the packing similar to the coating of the fiber of FIG. 9A by means of a binder 2. Such fillers 17 are used, for example, for filling mold cavities within molded bricks, eg bricks or mineral-bonded bricks.

According to another embodiment of the present invention petroleum coke particles are added foaming, which are used individually by the user. These are usually foamed by a blowing agent polymers or foams that are formed by reaction gases in the reaction of two-component systems. At e.g. polyurethane foams, one of the reaction components comprises the petroleum coke particles. The petroleum coke particles can be mixed into the polyol or isocyanate required for the reaction.

In the case of moisture-reactive polyurethanes (in particular in so-called assembly foams), the petroleum coke particles can also be added directly to the reaction component. When applied from the aerosol can, the petroleum coke particles are distributed in the membranes of the polyurethane foam and thus significantly improve the heat insulation during window or door frame mounting or other foaming operations.

The use of platelet-shaped petroleum coke particles, in particular of calcined petroleum coke, leads to a marked improvement in the thermal insulation effect with respect to the above-mentioned building materials. In addition, there is a clear shielding of electromagnetic radiation, so that the building material according to the invention in addition to the efficient thermal insulation also contributes to a reduction of the electromagnetic load (electrosmog). Furthermore, platelet-shaped petroleum coke particles have a synergistic effect with Flame retardants, with the result that the amount of flame retardants used can be reduced. The flame retardants are, in particular, organic bromine compounds or ammonium polyphosphate. The invention also provides a reduced tropi behavior in polymers.

BE TO G S SIGNATURE LIST

1) Particles

2) binders

3) cold-AVhair

4) fiber insulation mat

5) fiber

6) layer

7) layer

8) mold cavity

9) Plasterboard

10) outer layer

11) inner layer

12) layer of plaster

13) additional layer

14) molded stone

15) matrix

16) lamination

17) packing

19) Spiral jet mill

20) gas

21) nozzle

22) Electricity

23) air classifier

Claims

PATENT AT PRESS HE

Building material with heat-insulating property characterized in that the building material particles (1) of petroleum coke, in particular calcined

Petroleum coke, and it contains the building material around

a non-metallic-inorganic material and / or

a natural substance and / or

is a plastic other than polystyrene.

Building material according to claim 1, characterized in that the petroleum coke is formed isotropically.

Building material according to at least one of claims 1 or 2, characterized in that the petroleum coke particles (1) have a platelet-shaped grain shape. Building material according to at least one of the preceding claims, characterized in that the petroleum coke particles (1) have a specific surface area in the range of 3 to 50 m ² / g, preferably 3 to 35 m ² / g, particularly preferably 3 to 20 m ² / ,

Building material according to at least one of the preceding claims, characterized in that the petroleum coke particles (1) have an aspect ratio of 1-500, preferably 5-50, wherein the aspect ratio of the ratio of the average diameter to the average thicknesses of the particles (1).

6. Building material according to at least one of the preceding claims, characterized in that the petroleum coke particles (1) have a mean particle size of 1 μηι - 50 μη, preferably of 1 μπι - 10 μηι have.

7. Building material according to at least one of the preceding claims, characterized in that the petroleum coke particles (1) are comminuted in a spiral jet mill, preferably a hot gas jet mill.

Building material according to claim 7, characterized in that the spiral jet mill has an air classifier.

Building material according to at least one of the preceding claims, characterized in that the thermal conductivity of the building material in comparison to a corresponding building material without petroleum coke is reduced by at least 2.5%, preferably by at least 10%, particularly preferably by at least 20%.

Building material according to at least one of the preceding claims, characterized in that the petroleum coke is contained in an amount of 0.05 wt.% - 10 wt.% Based on the total weight of the building material.

11. Building material according to at least one of the preceding claims, characterized in that the building material comprises a binder (2) and the petroleum coke particles (1) are distributed in the binder (2).

12. Building material according to at least one of the preceding claims, characterized in that the building material has a coating containing petroleum coke particles (1).

13. Building material according to at least one of the preceding claims, characterized in that it is the building material to a fired molding with mold cavities (8) and the walls of the mold cavities (8) at least partially with a petroleum coke particles (1) containing coating are provided.

14. Building material according to at least one of the preceding claims, characterized in that it is the building material is a hydraulically bonded molding or a plaster-containing molding.

15. Building material according to at least one of the preceding claims, characterized in that it is the foamed polymeric material in the building material.

16. Building material according to at least one of the preceding claims, characterized in that it is the building material is a fiber, in particular a mineral fiber, and the fiber is provided with a coating, the particles (1) of petroleum coke, in particular calcined petroleum coke.

Building material according to at least one of the preceding claims, characterized in that the building material is a composite of individual fibers (5) which are bound together by means of a binder (2), and the particles (1) of petroleum coke, in particular calcined petroleum coke, are in the range of the binder (2).

18. Building material according to at least one of the preceding claims, characterized in that the building material is a particle (1) of petroleum coke, in particular calcined petroleum coke, coated packing (...), in particular filler made of pearlite, expanded clay, Vermiculite or mica.